NANOSELECT Résumé de rapport

Final Report Summary - NANOSELECT (Functional membranes/ filters with anti/low-fouling surfaces for water purification through selective adsorption on biobased nanocrystals and fibrils)

Executive Summary:NanoSelect project aim was to design, develop and optimize novel bio-based nanostructured polymer based membranes/adsorbents/filters with specific selectivity using surface active entities like nanocellulose, nanochitin and combinations thereof. These materials may be categorized as nano-enhanced membranes and used for decentralized industrial and domestic water treatments. Highly efficient water treatment products was attained via engineering permeable nanomembranes or nanoporous filters (based on existing nanostructured membrane, NSM technology) and further tailoring their ability to interact and selectively adsorb/store and desorb heavy metal ions, toxic chemicals and/or bacteria using nanoenabled membrane, (NEM) technologies. In the current project, we developed novel water purification strategies that employ bio-based nanoparticles to combine mechanisms of physical filtration, surface adsorption and a combination thereof, using biobased nanoparticles. The main outcome from the NanoSelect are• Isolation of cellulose nanocrystals and nanofibers from bioresidues and industrial side streams and their scaled up processing• Development of modified nanocellulose and nanochitin with enhanced interaction with water contaminants as dyes, nitrates and heavy metal ions• Development of bio-based nano-enhanced membranes using native and modified nanocellulose/ nanochitin and their combinations thereof with high efficiency and high selectivity for water treatment, with special focus on fertilizers, pesticides, heavy metal ions and microbial contaminants relevant in industrial water.• Recommendations for recovery of heavy metal ions after adsorption and composting of modules after nitrate adsorption• Recommendation for low/anti-fouling surfaces using nanocellulose technology• Development of biodegradable membranes which can be composted at end-of-life • Development of safe and cost-effective decentralised water cleaning technologies that can be applied in European process industries, urban water treatment plants and elsewhere.The demonstration of the modules and prototypes from Nanoselect was successful at the industrial sites and effectively reduced nitrates, dyes and suspended solids. The Nanoselect membranes and modules once scaled up was estimated to be competent in the market, for suspended solids (compared to PP filters) for dyes ( compared to activated carbon) and for nitrates (compared to resins) . Cost analysis showed that the use of Nanoselect nitrate filters have an added advantage over commercial membranes of due to adsorption efficiency as well as disposal potential as fertiliser. It was also clear that the membranes and modules from Nanoselect project once scaled up will lead to reliable margin and return of investment. The technology transfer to industries can be done effectively as the Nanoselect module design with a standard size which makes it easy to introduce and install these in the current market and existing installations. A collaboration between paper making industry and membrane industry can be recommended as a successful route for the optimization of the membrane and module processing and a fast market entry. NanoSelect project has resulted in new know-how on surface interaction of nanocellulose/nanochitin with different molecules, atoms and, ions, and is also expected to open up new applications and increased utilization of these bio based nanomaterials as functional materials, beyond water treatment application.

Project Context and Objectives:NanoSelect project aim was to design, develop and optimize novel bio-based nanostructured polymer based membranes/adsorbents/filters with specific selectivity using surface active entities like nanocellulose, nanochitin and combinations thereof. Development of new know-how on surface interaction of nanocellulose/nanochitin with different molecules, atoms and, ions, and new applications and increased utilization of these bio based nanomaterials as functional materials, beyond water treatment application was also aimed at.

In reporting period 1, the main objectives were isolation of nanocellulose and nanochitin from bioresidues, and screening of materials based on surface interaction with water contaminants. The nanocellulose and nanochitin were also modified with anionic and cationic functionalities to achieve increased interactions with contaminants in water. The scaling up of the nanoparticle processing in an energy efficient and cost efficient way. Different processing routes for membrane, and filter processing as attempted and screened for optimal performance and potential for scaled up.The project objectives of period 2 was to use nanocellulose scaled up during the report period I and their modified versions to prepare membranes and adsorbants for water purification. The processing and characterisation of membranes and adsorbants, evaluation of the interaction and adsorption potential, and validation of the materials for scaling up and prototype development were the main objectives of this period. The evaluation of reuse of membranes, degradation of membranes in use conditions and during composting was also planned for this period. In addition, the LCA analysis of the developed membranes as well as market and cost analysis of the nanomaterials were envisioned . The dissemination activities planned included publication of results, active participation in nano4water and organisation of nano4water workshop.The project objectives of reporting period 3 were to optimise the membrane processing based on the results and knowhow from earlier reporting periods and also to scale up the membranes for the module processing and final demonstration. The processing and characterisation of membranes and adsorbents, evaluation of the interaction and adsorption potential, and validation of the materials for scaling up and prototype development were planned. The demonstration of the membranes in lab scale for adsorption and antifouling performance as well as the demonstration of the scaled up membranes and prototypes at industrial sites were planned during this period. In addition, the LCA analysis of the developed membranes, market and cost analysis as well as external technology transfer plan were evaluated and established during this period. The dissemination activities planned included publication of results as journal papers, PhD thesis, popular science write ups, press releases, and presentations of results in conferences and seminars. The final plan for dissemination and exploitation was also developed during this period.

The project achieved the goals set at the project start and the technology is developed beyond the state-of-the- art at different levels. Isolation of nanoparticles from bioresources and the process scaling up is done successfully. Cellulose nanocrystals processing is scaled up to a rate of 600 gms /day and cellulose nanofibers to a rate of 15 kg/ day. The main advantage of the process is the use of industrial residues and the integration of the process with already existing industrial processes or pilot scale processes in forest industries. The processing cost of nanocellulose developed in Nanoselect was calculated based on bench scale process and was found to be 30Euros/ Kg for CNCBE and 5 Euros/ Kg for CNFSL. The prices are expected to be further decreased when production volumes are increasedThe biobased nanoparticles showed adsorption capability to heavy metal ions from water, the adsorption capability being in the order Cellulose nanocrystals from bioethanol (CNCBE) >Cellulose nanocrystals from sludge(CNCSL) > Chitin nanocrystals (ChNC) > Cellulose nanofbers (CNF) (for Ag+). The nanocellulose and nanochitin can be therefore used as efficient and environmental friendly functional material in water purification.Surface modification of the nanoparticles provided increased adsorption efficiency or specific selectivity towards contaminants. Negatively charged nanocelluloses have been prepared through a Tempo-mediated oxidation of the sludge and chitin followed by mechanical disintegration. Positively charged nanocelluloses, ie Cationic nanocelluloses with increasing positively charged ammonium groups have been prepared from the sludge, according to a water-based modification protocol with with glycidyltrimethylammonium chloride (EPTMAC) and subsequent mechanical disintegration.The membranes with and with out modifications were developed and scaled up by Nanoselect team have the capability to remove heavy metal ions, dyes, humic acid , nitrates, sulphates, etc Hybrid nanopapers or bilayered membranes from renewable nanomaterials and sludge as well as modified nanocellulose have been developed. In general the evaluation of foulants from water sources showed that biofouling is the major cause for fouling in membrane filtration planned in Nanoselect, The WP5 activities were therefore focused on developing membranes that are resistant to bacterial adhesion and biofouling. From the evaluation of membrane fouling with model bacteria solutions, it was concluded that low bacteria adhesion, no biofilm formation and few colonies development were observed for chemically modified membranes developed with in Nanoselect project meaning that these material could posses antifouling properties which are superior to commercial cellulose based membranes. Furthermore, nanocellulose based membranes were found to be inherently antifouling due to its hydrophilic nature and can be used as antifouling membranes without additional surface functionalizationMembrane assemblies and modules based on selected modified and unmodified nanocellulose were validated for removal of dyes, metal ions and nitrates, as well as recovery of metal ions and reuse of membrane modules. The demonstration of the modules and prototypes from Nanoselect was successful at the industrial sites and effectively reduced nitrates, dyes and suspended solids. The Nanoselect membranes and modules once scaled up was estimated to be competent in the market, for suspended solids (compared to PP filters) for dyes ( compared to activated carbon) and for nitrates (compared to resins) . Cost analysis showed that the use of Nanoselect nitrate filters have an added advantage over commercial membranes of due to adsorption efficiency as well as disposal potential as fertiliser. It was also clear that the membranes and modules from Nanoselect project once scaled up will lead to reliable margin and return of investment. The technology transfer to industries can be done effectively as the Nanoselect module design with a standard size which makes it easy to introduce and install these in the current market and existing installations. A collaboration between paper making industry and membrane industry can be recommended as a successful route for the optimization of the membrane and module processing and a fast market entry.

The results from the project are disseminated adequately through peer reviewed journal articles, PhD thesis, seminar and conference contributions, workshops (Nano4water), popular science publications, newsletters, web site (www.nanoselect.eu) , facebook, newsletters, etc . Networking seminars were organised during the project period which the interaction between the researchers and industry partners. Active exchange of researchers , infrastructure and materials between partners occurred during the project and is expected to continue even after the project end.One patent is filed and an agreement is executed on ownership of the final working prototype to clearly define the IP rights The IP generated from the project will be used as background for other national and EU projects by all partners.

Project Results: The main science and technological developments and the foreground from Nanoselect the project is summarised under the respective work pages. (All Figures, Tables and Videos are available under Appendix 1)

WP2. Isolation and characterisation of nanoparticles from bioresources and residuesThe raw materials as wood residue, sludge form cellulose production, crabshell residue were used for nanoparticle isolation. The methods used to prepare cellulose nanocrystals (CNCSL, CNCBE), cellulose nanofibers (CNFSL) and chitin nanocrystals (ChNC) are shown in Fig. 1.

Fig.1 Procedures for isolations of nanocellulose and nanochitin

The AFM images in Fig.1 show the typical morphology, size distribution and diameters of CNC, CNFs and ChNC . CNC/CNCBE and ChNC displays rod-like shape with diameters in the range of 5 - 10 nm and 11 - 40 nm, respectively, as measured by Nanoscope V software. The diameter of CNF is in the range of 15-70 nm, while the length is estimated to be several microns as an accurate measurement using AFM was not possible. The nanoparticle had different surface groups based on the source and isolation route. See Table 1 for details.

TABLE 1. Physiochemical characteristics of CNF, CNC and ChNC

A surface charge density of 230 μmol/g has been calculated for CNC from the neutralization point obtained from the titration curve (See Table 2). This value is in the same order as the surface charge of cellulose nanocrystals extracted from industrial bio-residue and commercial microcrystalline cellulose, with reported surface charges of 148±11 μmol/g and 259±39 μmol/g, respectively. The surface charge of CNF was lower (100 μmol/g) while that of ChNC were higher (320 μmol/g) compared to CNC. Surface charge on ChNC is due to both positively and negatively charged entities.

Figure 2. Zeta potential as a function of pH

Zeta potential refers to the surface electric potential of the colloidal particles suspended in aqueous environment, and can be considered as an indication of the surface charge of colloidal particles. Zeta potentials of CNC, CNF and ChNC show a dependence on pH conditions as shown in Fig. 2. Zeta potential was found to be powerful tool to understand the adsorption potential of prepared nanomaterials and the scaled up nanomaterials (CNCBE and CNFSL were evaluated and compared to the modified versions. See Figure 3a and 3b. It was found that all these nanoparticles have a negative zeta potential value indicating the possibility to interact with positive species as metal ions and dyes in water.

Figure 3: Zeta potentials a) of bioethanol CNC, CNC (sludge), phosphorylated CNC and phosphorylated CNF b) CNF and Tempo oxidised CNF with different carboxylic group contents at different pHIt was found that CNCBE scaled up using bioethanol process route has high negative surface potential compared to CNCSL prepared via sulphuric acid hydrolysis. To understand this behaviour the surface properties were studies using XPS and the results are shown below in Figure 4 . It was found that CNCBE have significantly higher concentration s of carboxyl groups on its surface, which is considered a great advantage for adsorption of positively charged species. It was also considered a great advantage that the negative charge is high even with out additional surface modification.

Evaluation of the interaction of cellulose/chitin nanocrystals and cellulose nanofibrils surfaces with water heavy metal ions

The potential of cellulose nanocrystals (CNC), cellulose nanofibers (CNF) and chitin nanocrystals (ChNC) isolated from bioresidues to remove positively charged metal ions from contaminated water were evaluated ( See Figure 5) . Contaminated water after treatment with CNC, CNF and ChNC suspensions and filtration showed a significant decrease in Ag+ ion concentration as measured by ICP- OES (inductively coupled plasma mass spectrometry). The highest metal ions removal measured at near neutral pH for CNC, followed by ChNC and CNF. The WDX (Wavelength dispersive X-ray analysis) and XPS (X-ray photoelectron spectroscopy) data also supported the ICP-OES study and confirmed the adsorption of silver ions on the nanomaterials.

The ICP–OES results show that all the three bionanomaterials showed potential for Ag+ adsorption. Above a pH of 4.8 the highest for cellulose nanocrystals, followed by chitin nanocrystals and the least for cellulose nanofibers. At lower pHs, ChNC showed highest adsorption. The ICP-OES, WDX and XPS data clearly show that Ag+ ions can be adsorbed on the surface of nanocellulose and nanochitin, the adsorption capability being in the order of CNC >ChNC>CNF. The highest adsorption measured in our conditions was 34.38mg/g for CNC.

Scaled up processing of nanocelluloseA large scale super masscolloider/ultra fine grinder up to 1000 kg/hours have been purchased and installed with an aim to demonstrate cellulose nanofiber processing in larger scale (See Figure 6).

Figure 6: Masuko MKZA 10-20J, installed at LTU

The schematic representation of the process for scaled up processing of CNF and CNC is given below (Figure 7). The nanocellulloses will be used in membrane processes.

Figure 7: Schematic representation of scaled up processing of CNF and CNC, at LTU

Isolation of nanoparticles from bioresources and the process scaling up is done successfully. Cellulose nanocrystals processing is scaled up to a rate of 600 gms /day and cellulose nanofibers to a rate of 15 kg/ day. The main advantage of the process is the use of industrial residues and the integration of the process with already existing industrial processes or pilot scale processes in forest industries. Scaled up nanocellulose processing of nanocellulose was demonstrated at LTU on 27 Aug 2013. The processing cost of nanocellulose developed in Nanoselect was calculated based on bench scale process and was found to be 30Euros/ Kg for CNCBE and 5 Euros/ Kg for CNFSL. The prices are expected to be further decreased when production volumes are increased. Though the comparison of cost is not easy due to lack of accurate public information on price, it can be seen that the cost estimated for Nanoselect CNF is significantly lower than the price of commercial CNF from other sources: Eg 100 USD / kg for 3 wt% suspensions from University of Maines. The cost of CNC from University of Maines was 500 USD / kg for 12 wt% aqueous suspensions. The lowest price announced for nanocellulose till date is from Univeristy of Maine, with a price as low as 30 USD/ kg an is still significantly higher than the estimated cost of CNF according to Nanoselect process.

WP3Surface modification strategies for nanocellulose and nanochitinCellulose nanofibers with negative charges (carboxylate groups) on their surface are prepared either via TEMPO-mediated oxidation of the wood pulp followed by mechanical disintegration or via reaction of the wood pulp with anhydrides followed by mechanical disintegration. Negatively charged nanofibers are then subsequently used for the uptake of heavy metal ions (Cu2+, Cr3+, Zn2+, Ni2+) in solution. Cellulose nanofibers with phosphate groups on their surface are also prepared and characterized with respect to their capacity to adsorb Ag+, Cu2+ and Fe3+. Cellulose nanofibers with positive charges on their surface are prepared by reacting a quaternary ammonium with the wood pulp followed by mechanical disintegration and used for anions adsorption (nitrate, fluoride, sulphate and phosphate) and for the uptake of a natural organic matter (humic acid). Other possible strategies for water decontamination, including the combination of cellulose nanofibers and nano-zero valent iron (nZVI), or chitin deacetylation are also attempted. The possibility of contaminants desorption from the nanofibers and their possible reuse are also looked at. The list of modified nanomaterials developed in the project are:

In situ surface modification of membranesOriginally the nScrypt direct-write microdispensing environment was evaluated as a method for surface modification of membrane structures. nScrypt system was verified to be suitable for dispensing modified polysaccharides, such as TEMPO oxidized cellulose and allylated xylan derivatives for membrane surface modification. This approach may however lead to heterogeneous modification and it will result uneven mass transfer in membrane, which can be considered to be an unwanted feature

The alternative membrane surface modification method via TEMPO oxidation was chosen to increase the functionality, especially anionic surface charge of the membranes. Nanocellulosic membrane structures were surface modified using TEMPO oxidation with subsequent NaClO2 treatment. It was found out that highly anionic nanofibrils and films have ion capturing ability and furthermore, numerous carboxylic acid groups can be used for further modifications.TEMPO modification was performed on Nanoselect membranes by VTT as shown in Figure 8.

Figure. 8: In situ functionalization of top layer was performed as shown in image. The symbol x represent a monomer of cellulose.

The functionalization of top layer after fabrication of membranes is a new concept. This approach might be helpful to increase the adsorption capacity of fabricated membranes. Easy availability of anchoring sites to bind pollutants seems to increase the adsorption capacity.

Adsorption characterisationThe general strategy pursued for the uptake of contaminants is based on electrostatic interactions whereby functional nanofibers adsorb entities of opposite charges. The absorption capacity and selectivity of the modified nanomaterials have been evaluated and it was clearly demonstrated that Surface modification of the nanoparticles provided increased adsorption efficiency or specific selectivity towards contaminants.

Negatively charged nanocelluloses prepared through a Tempo-mediated oxidation of the sludge and chitin was used for meal ions ions capture. The increase in copper adsorption on the nanofibers correlated both with the pH and carboxylate content and reached maximum values of 135 mg g-1 and 55 mg g-1 for highly oxidized cellulose and chitin nanofibers, respectively. Four metal ions have been studied in this work: Cu(II), Ni(II), Cr(III) and Zn(II). Cellulose nanofibers (CNF) and chitin nanofibers (ChNF) had a relatively low amount of functionalities on their surface resulting in low Cu2+ adsorption capacities (27 mg/g for ChNF vs 13 mg/g for CNF). Introduction of carboxylates groups onto the surface of the nanofibers through TEMPO-mediated oxidation proved to be a facile functionalization route that enhanced considerably their copper adsorption through electrostatic interactions. The Cu(II) adsorption was found to increase linearly with the carboxylate content (Fig.9). The nanoscale structures of the nanofibers resulted in a fast adsorption of copper onto the biobased nanomaterials, which is in the order of a minute. Figure. 9 Photograph of nanofiber filter cakes after Cu(II) adsorption for different pH with different surface chargeFinally, the following adsorption capacities have been measured for oxidized cellulose nanofibers: Cr3+ (58 mg.g-1), Ni2+ (49 mg.g-1) and Zn2+ (66 mg.g-1). Furthermore, the metal ions could be easily removed from the contaminated nanofibers through a washing procedure in acidic waterIt was also noticed that adsorbed copper ions on the surface subsequently self-assemble to copper nanoclusters with a rather narrow size distribution, which provides a promising probability of converting the TOCNF saturated with copper nanoclusters into a variety of value-added products. TOCNF coupled with adsorbed copper exhibited superhydrophilicity (Fig. 10). The filtration time for the TOCNF suspension after copper adsorption was substantially shortened and even comparable to pure water. All of the above variations in the properties of TOCNF during copper adsorption present a great promise from the perspective of industry for TOCNF commercialization as either a dispersed adsorbent or a functional layer in a composite membrane for water remediation.Figure. 10 Contact angle variation with Cu(II) adsorption on TOCNF Unmodified (CNCSL, CNCBE) and the modified nanocelluloses (phos-CNCBE and phos-CNFSL) showed potential for immobilization of Ag+, Cu2+ and Fe3+. The primary functional groups on the surface, which are regarded as the chemical active sites that are capturing metal ions, are sulfonate group (CNCSL), carboxyl group (CNCBE) and phosphate group (phos-CNCBE and phos-CNFSL). The metal ions removal efficiency of the four nanocelluloses follows the same sequence: phos-CNCBE > phos-CNFSL > CNCBE > CNCSL. Phos-CNCBE and phos-CNFSL immobilized nearly 100 % of the Ag+, Cu2+ and Fe3+ in the aqueous solutions. The adsorption selectivity (or competitive adsorption) towards the metal ions (Ag+ > Fe3+ > Cu2+) by all the studied nanocelluloses is shown in Fig. 11. Phosphorylated cellulose displayed the capacity to slash Cu2+ and Fe3+ concentrations in mirror industrial effluent to the levels that meets drinking water requirements. Figure.11 Effect of single ions vs multiple ions in the water on the adsorption selectivity of Ag+, Cu2+, Fe3+ on the nanocelluloses at pH 3.5–4.5. Figure 12 shows the adsorption behaviour of native and modified nanocellulose in industrial effluent from mirror industry (provided by Acondaqua). Phos-CNCSL and phos-CNFSL have the capacity to slash Cu2+ and Fe3+ concentrations in industrial effluent to the levels that meets national drinking water requirements (see the table in Figure 12a). Figure 12b compares the removal efficiency as a function of surface characteristics and shows complete (99-100%) removal of the metal ions by phosphorylated nanocellulose. The experimental results clearly display that nanocellulose can remove Cu2+ and Fe3+ ions not only from model water, but also from industrial effluent, particularly when using phosphorylated nanocelluloses.Figure 12. Scheme showing the industrial effluent and the effect of treatment with nanocelluloses on the ion concentration

The same methodology has been applied for the synthesis of acid-functionalized nanocelluloses, through a prior esterification of the sludge with anhydrides followed by mechanical disintegration. Maleic, succinic and phtalic anhydrides have been tested. Above the pKa of the acid-terminated function, the functionalized nanofibers proved to be efficient in capturing Cr3+ (35-75 mg.g-1), Ni2+ (20-50 mg.g-1), Zn2+ (35-60 mg.g-1) and Cu2+ (40-65 mg.g-1). Positively charged nanocelluloses, ie Cationic nanocelluloses with increasing positively charged ammonium groups have been prepared from the sludge, according to a water-based modification protocol with with glycidyltrimethylammonium chloride (EPTMAC) and subsequent mechanical disintegration. Cationic cellulose nanofibers showed promising results towards removal of nitrates (NO3-) from contaminated water at neutral pH.WP4 Fabrication of membranes/ foams or porous structures Two process routes were successful for the preparation of membranes• Hybrid nanopapers from unmodified or modified nanomaterials and sludge have been developed. These high-flux membranes can be applied as adsorbent membranes for heavy metal ions for the purification of wastewater. This procedure was also used for scaled up membrane process and prototyping.

• Bilayered membranes with sludge or sludge/ CNF as support layer and functional nanocellulose (CNCBE, cationic CNF, tempo CNF) and was found to have a good balance of mechanical properties, permeation and functionality and were optimised further for scale up and prototyping.

To achieve improved pore size control and mechanical strength, palygorskite (PGS) which is a type of natural nanoclay has been incorporated into CNF to produce nanocomposite membranes. Other types of nanofillers including 3-YSZ 3-YSZ (3 mol% yttria stabilized zirconia).γ-Al2O3 (Gamma alumina) and UiO-66 (a type of Metal Organic Framework, MOF) have been used as additives and incorporated into CNF to produce nanocomposite membranes.

Adsorption performance of the membranes

a) Dyes removal using CNC membranes: The results shown in Figure 14 gives us a indication that our hypothesis is working. Complete removal of victoria blue 2B dye was recorded by prepared membrane (including 0.2% chitosan). All selected dyes were highly hazardous according to the EPA report. The adsorption experiment was performed in static mode, which gives less availability of functional groups, thus in future it is compulsory to run the adsorption experiment in dynamic mode.

Figure 14: Three dyes as mentioned in table were selected for the removal experiment. Adsorption experiment was conducted in static mode.

b) Removal of metal ions from mirror industry effluents using layered membranes: Mirror industry effluent laden with metal ions (Ag+ and Cu2+/Fe3+/Fe2+) when treated with cellulose nanocomposite membranes with anionic charge, showed high ion removal capacity, being 100% for PCNCSL followed by CNCBE than CNCSL. The removal of metal ions was expected to be driven by interaction between negatively charged nanocellulose and the positively charged metal ions. See Table 2 below.

Table 2: ICE-OPS analysis of metal ions removal

c) Removal of nitrates using hybrid membranes: The cellulose nanofibrils were modified with quaternary trimethylammonium groups cationic nanopaper ion-exchangers was assessed with respect to their permeance and nitrate adsorption. Nitrates could be successfully captured onto the cationic nanopaper and thus rejected from contaminated water during dynamic filtration experiments. The ion-exchange nanopaper had adsorption capacities in the range of commercial available adsorbers but with the advantage of reduced contact time.

It was found that nanopapers containing ammonium moieties were able to adsorb nitrates up to 390 mg per m2 filtration area equivalent to an adsorption capacity of more than 12 mg nitrate per g active adsorption agent. These experiments also showed that the contribution of nitrate adsorption by quaternary ammonium groups on the surface of the nanopaper is probably higher than that of functional groups in the bulk of the nanopapers. We showed that nanopapers containing cationic cellulose nanofibers are efficient as ion exchange nanopapers allowing for nitrate removal from contaminated water. It can be concluded that an even higher concentration of ammonium groups on the surface of thin nanopapers should result in an even higher efficiency; i.e. exhibit a higher nitrate “rejection”.

Modelling of permeance and transport through membranes

Modelling of the permeance showed that the CNF support layer used in layered membranes is responsible for the majority of the resistance to flux and the flux may improved by increasing the porosity or decreasing the thickness of this layer. In the case of multilayered membranes flux resistance lies within the support layer for these membranes and is possible to further enhance the flux by increase the pore size or decrease the thickness of this layer, provided that the mechanical strength still remain sufficient.

Figure 15: Schematic figure of layered membrane structure and pressure profile.Modelling of adsorptionThe predominant mechanism of contaminant removal in all studied membranes and in all contaminants is the electrostatic interaction between the nanocellulose surfaces and the contaminant. Surface adsorption followed by micro-precipitation was also found to be a possible mechanism of ion removal, which opens up a new generation of ultrafiltration membranes with high selectivity towards ions. DFT computational studies reveals a possibility for clustering of Ag to a PO3-functionalised cellulose surface ( See figure 16) . A stable structure could be obtained for up to 20 silver atoms to a 4x84 atom cellulose system. Binding energy when adding the 20th silver atom was calculated to 202 kJmol-1, which indicate a further ability for coordination of more silver atoms. Calculated IR-spectra supports the experimental observation of shifting of P-O stretch vibrations towards a higher frequency upon coordination of silver atom to the PO3-group.

Figure 16. DFT model for the cluster formation of Ag on celulose surfaces with phosphoryl groups.

• WP5 Development and evaluation of antifouling membranesAntifouling strategies for the membranes and recovery of chemicals. And also the possibility to reuse membranes after adsorption was also evaluated. The major foulant in the water sources of interest was found to be biofouling. So focus is laid on increasing the resistance of the membranes and adsorbants towards biofouling.Three major approaches have been selected to inhibit surface biofouling based on preventing foulants from attaching and the degradation of these foulants.• Surface membrane functionalization with antibacterial quaternary ammonium salt (QAS).• Polymer grafting to surface membrane (polymers “brushes”).• Modification of the surface charge on nanochitin via deacetylation

From the evaluation with model bacteria solutions, it can be concluded that low bacteria adhesion, no biofilm formation and few colonies development were observed for QAS functionalized CNF, cationic CNF and NChitin membranes, indicating that that these material could posses antifouling properties which are superior to commercial cellulose based membranes

VTT has focused on developing ion-exchange membranes/ materials with antifouling properties. Antifouling strategy of membranes via thermoresponsive poly(N-isopropylacrylamide), pNIPAM, has been developed and several routes have been mastered. pNIPAM undergoes a change in hydration state at 32-34 °C which is assumed to have effect on the adhesion of foulants. The most promising modification strategy seems to be the surface modification of CNF based membranes, for example, first TEMPO oxidation conducted on a cellulosic membrane surface, then esterification of that, and finally a direct reaction of activated TEMPO CNFs with so-called amine terminated poly(N-isopropylacrylamide) which is available also as a commercial product. Polyvinyl alcohol can be utilised as strength additive also in this approach. Temperature effect on relative flux of TEMPO CNF-PVA membranes with pNIPAM group has been investigated by Imperial group, and for the first time the changes in relative permeances as a function of temperature was detected. Nanocellulose based membranes were found to be inherently antifouling due to its hydrophilic nature and can be used as antifouling membranes without additional surface functionalization. Evaluation of antifouling properties in real water could not be properly evaluated due to the combination of contaminants adsorption and membrane degradation due to the presence of bacteria. Strategies for recovery of chemicals and reuse of filtersIn this period, Cemitec has been working on the recovery of metals, in particular copper, and nitrates adsorbed on the Nanoselect membranes.The basic principle used in this project for capturing-recovery heavy metal and nitrate ions is the use of oppositely charged functional groups. On the one side, cationic metal ions for example silver (Ag+), lead (Pb2+), copper (Cu2+) and arsenic (As5+), can be captured by carboxyl groups of TEMPO-CNF and can be detached by washing the membrane with acidic solution. On the other side, negative ions, such as nitrates, can be captured by cationic groups of cationic-CNF and detached by washing with basic solution.

Heavy metals recovery study confirms that it is possible to recover copper from TEMPO-CNF membranes washing them with an acid solution and maintaining this capture capacity after the recovery. Two different studies have been carried out in order to evaluate the recovery of copper from TEMPO-CNF membranes. In a first approach, copper was adsorbed on aqueous dispersed TEMPO-CNF and recovered by dispersion of the membrane nanofibers in water. The result of this study shows the highest adsorption and recovery capacity of the material. In a second approach, copper was adsorbed in already prepared TEMPO-CNF membranes and recovered by passing an acid solution thought the membrane. The results of this study are closer to the real filtration conditions. The removal of silver ions from bilayered membranes were also evaluated. Although the percentage of adsorbed and desorbed amount of Ag+ in the bilayered membranes are lower than in the case of Cu, in dispersed fibers and monolayers membranes; the adsorption capacity was kept and the cations adsorbed could be recovered. The use of nitric acid shows a better efficiency in the recovery than the hydrochloric acid because it does not cause the precipitation of silver salts and therefore a higher amount of cations can be recovered. Evenmore, incineration can be carried out after its used in order to recover to 100% of the adsorbed heavy metals.

Nitrates recovery experiments were also performed with an alkali solution, making possible the recovery of this type of compounds. In these recovery experiments it was noticed that adsorption – desorption ability in membranes is lower than the ability shown by dispersed nanoparticles. It can also be concluded that nitrate adsorption capacity of the cellulosic materials depend on the experiment conditions. When the adsorption-recovery experiments were carried out in already prepared membranes the nitrate adsorption ability of the fibers is significantly reduced in comparison with the experiments carried out with redispersed membranes. Recovery experiments in dispersed fibers show that 67% of the adsorbed nitrates can be recovered after washing the cationic nanofibers with the alkali solution. A similar percentage was reached in the experiments carried out with corresponding membranes. However the amount of nitrates (mmol NO3-N) per gram of CNF is considerably lower, 10 vs 1 mmol NO3-N.

• WP6Life cycle analysisLife cycle assessment has been performed for four flat sheet membranes to assess their environmental performance. Calculations have been carried out with SULCA software, based on the inventory of relevant inputs and outputs during the lifecycle of the products (energy, raw materials, membrane production, membrane operation). The functional unit is 1 m3 of treated water.

Life-cycle assessment results show that the production of nano-materials and the use phase of the membrane are the dominant areas of environmental impacts. Especially the production of Tempo oxidised CNF seems to have high impact. Manufacturing nanomaterials at small scale is energy intensive and efficiency gains are likely to be realised with larger-scale processes.The use of CNC(bioethanol) shows higher environmental impacts than use of CNF(sludge). Large amount of chemicals used in the lab-scale biorefining process producing raw material for CNC is a main contributor of the environmental impacts as shown in Figure 17.

For spiral wound modules the use of plastic materials (centre shaft, spacers) is the dominant area of the cradle-to-gate life-cycle environmental impacts. Further research on the optimization towards environmental improvement/ fully bio-based modules should be conducted.

The level of uncertainty of lab-scale data used in this study must be taken into account when communicating information outside the consortium. For LCAs on emerging technologies, such as NanoSelect, considerable amount of secondary and proxy data must be utilised. Data collection for lab scale processes is challenging: Use of unfamiliar /novel materials for which LCI data is not available cause uncertainty in the results, as well as the fact that necessary measurements needed for a full life cycle inventory are lacking in the lab-scale processes (e.g. emissions to air and water).

Safety analysis of the membranesThe safety analysis of the Nanoselect membranes was evaluated via biodegradation studies in 1) real wáter containing heavy metal ions 2) real wáter containing nitrates, organic contaminants ad microorganisms and 3) soil .The visual illustration of the membranes as shown in Figure 18 at different stages of biodegradation study confirms the zero degradation rate in polluted water for all samples. The used real wastewater from mining industry was not a suitable habitat for microorganism to grow, thus, this effluent doesn’t contain any living microorganism. Therefore, the predominant factor, which might be responsible for the increase rate of degradation, is pH but no sign of weight loss is reported up to 30 days.

Figure 18: Biodegradability study of fabricated nanopapers in water (a) and in soil (b).

This confirmed the potential to use the membranes safely in water with different pH conditions. However, the membranes degraded in water within 2 weeks when microorganisms are present, except for cationic membranes, which were found to be resistant to bacterial attack. Degradation studies shows that CNF membranes and NChitin membranes are partially degraded by bacteria in waste water, while Cationic CNF membranes are not affected.The membranes degraded in soil with in 4 months and can potentially be dispose by composting after use. See figure that illustrates the biodegradation study of composite in soil. Complete degradation of support with and without CNF was recorded after 15 days but 92% and 87% degradation was achieved for modified composite membranes (See Figure 18) .Technology transfer planCemitec worked during this period (M37-M48) for establishing the Internal Technology Transfer Plan (ITTP). For all of exploitable results, it was defined that it will be necessary to sign a specific declaration of interests about technology and product, together with the warranties needed in order to set up the transfer system. In those cases in which different partners were interested in patenting, it will be also necessary to sign agreements in which the conditions of the patent will be defined, who will be the inventor, the financial contribution, and other considered issues.The external technology transfer plan is prepared during M45-48 by Acondaqua and Alfalaval. The following conclusions are reached in the plan,• Adopting the Alfa Laval PROMAL process for the Nanoselect project, the development status of the different products under development are in the feasibility/pre-study stage, underlining the need for further development before commercialization/full exploitation• A collaboration between paper making industry and membrane industry can be recommended as a successful route for the optimization of the membrane and module processing and a fast market entry.• It is possible to produce Nanoselect membrane and customise the functionality for targeted contaminants by changing the type of the nanocellulose material. The membrane and module processing once scaled up can be effectively adopted by industries with dyes, nitrates and suspended solids contamination• Technology transfer to industries can be done effectively due to the Nanoselect module design developed with a standard size so that it is easy to introduce and install it in the current market and existing installations.

WP7Based on the feed back from lab scale demonstration at VTT and field test trials by Acondaqua , optimizations of composite membranes and module design have been attempted. Scaled up nanopaper with varied functionalities were produced at MoRe Research at Örnsköldsvik, Sweden, using their experimental paper machine (XPM). These membranes were then made into prototype with a spiral wound design for cartridge module with a pilot rolling machine. The modules have been sent off to Acondaqua for the demonstration of prototypes for water cleaning under WP8. Prototype of spiral wound module and cartridge module has been designed and developed in a pilot scale for real time testing. Scaling up and optimization of membrane processing Though scaling up of the membranes were not initially planned, it was decided based on 42M meeting that to effectively demonstrate the membrane functionality and membrane homogeneity at industrial sites, pilot scale processing is required. So additional funds were allocated for this activity in consultation with EC Ares(2015)3745712 - RE: NANOSELECT 42 M Meeting. This activity was performed by LTU and Imperial researchers and the cost of the activity was shared between these partners.

To move on to pilot scale, the nanopaper production was collaborated with MoRe Research at Örnsköldsvik, Sweden, using their experimental paper machine (XPM), see Figure 19. The XPM can produce paper in a continuous roll of tens of metres in grammages between 20 and 300 g/m2. The paper machine has a width of 225 mm with a fourdrinier wire, a press section, a drying cylinder section with the same heat as large paper machines and with a yankee cylinder for production of tissue as well as paper. Additional equipment includes a conical refiner, four machine chests and equipment for dosage of chemicals at different positions. The paper is wound up onto a reel for later coating or surface treatment.

Figure 19. Experimental paper machine (XPM) at MoRe Research

Nanopaper produced with the XPM appeared to have consistent homogeneity and thus it was a viable way to scale up the membrane production.

Optimization of the module design Various designs of spiral wound module and cartridge module have been developed and sent for field-testing and validation at lab bench scale at VTT laboratory as well as the field testing and demonstrations. After field tests it was found that prototype with a spiral wound design for cartridge module had the best performance and therefore adopted for producing modules with the scaled up membranes. For the hybrid nanopapers, the modules were made with pass through mode to maximise the capacity for dynamic adsorption as these nanopapers had considerably high flux. For the coated nanopaper, pass over mode. The modules were made with a pilot rolling machine.. Each module consisted of 4 m of nanopaper and four modules were produced for each type of nanopaper.

Real time testing protocolThe first generation prototype shown in Figure 20 is used for the testing of the modules and optimising the protocol, iteratively.

Figure 20: Photograph of the generation 1 prototype for point-of- use water treatment.

The following cases were considered for the testis and optimization of the protocols1. Nitrates & Sulphates from well water/drinking water; 2. Nitrates & Sulphates from effluent of biological waste water treatment plant3. Dyes from waste water of Leather Industry4. Metals (Cr+3) from waste water of Leather IndustryIn all cases the mechanical stability of all filters/membranes has in general shown a good behaviour and the retention of solids has been good in general terms. Initial tests showed that although some reductions in contaminants have been detected, increasing the capacity of the membranes to retain/adsorb the target contaminants is required to reach commercially relevant reduction in contaminant concentrations. Therefore the membranes and module processing were improved and used for the final tests as well as the demonstrations.

• WP8.Demonstration of scaled up production of nanocellulose (LTU/Processum)The demonstration of scaled up processing of Cellulose nanocrystals from cellulose refined from bioethanol process by homogenization was conducted at LTU facilities on 27th August 2013. The scaled up mechanical fibrillation of cellulose sludge from special cellulose productions into cellulose nanofibers using Masuko 10-20J was also demonstrated at LTU on 27th Aug 2013. The process capacity of CNC is estimated to be about 600 gms/day and that of CNF to be 15 kg/ day.

Demonstration of membrane with antifouling surfaces and recovery of chemicals (VTT)During 36M demonstrations of the membranes at lab scale were carried out. The demonstration site was VTT Jyväskylä where adsorption and recovery of chemicals were demonstrated. Membrane modules for adsorption of dyes, nitrates and metal ions were provided by ICL, LTU and VTT. Sheets were constructed as spiral wound membrane modules and fitted to commercial cartridge housing at ICL. The tests included• Dye removal with CNCBE –membrane with dyes samples from tannery (real waste water source) from Acondaqua.: CNCBE membrane module combined microfiltration and adsorption, however adsorption was short-term. Suspended solids removal was 60% at the beginning of filtration and 39% at the end of the short filtration of dye sample. Maximum removal of chemical oxygen demand and colour was 27% and 40%, respectively. Sulphide analysed as sulphur was removed at 29% removal percentage. Removal of cations such as calcium, magnesium, copper and aluminium was obtained at 39 – 56% in the beginning of filtration. • Copper ion removal with TEMPO CNF and TEMPO CNF-PVA –membranes using copper sulphate solution: Protocol by CEMITEC will be used for copper ion recovery by acid wash. Tempo-PVA membrane showed slightly better copper adsorption than Tempo-CNF membrane. The capture of copper by the Tempo-PVA and Tempo CNF membrane module from the feed solution was 37% and 22% in the first adsorption stage, and 25% and 15% in the second adsorption stage, respectively. Recovery of copper was achieved from both Tempo membrane modules using 0.2% hydrochloric acid at pH of 1.5.• Nitrate and sulphate removal with Cationic CNF –membrane using water from contaminated well received from Acondaqua.: Cationic CNF membrane module removed some of the nitrate and sulphate ions. Maximum removal of nitrate and sulphate was 22% and 20%, respectively. However, the adsorption in one pass filtration was short-term and concentrations increased quite rapidly.

Demonstration of prototypes for water cleaning (Alfalaval, Acondaqua)Prototype design optimization performed and demonstration was conduced at the industry sites during M48. Different tests have been performed to remove targetted contaminants with the membranes rom industrial effluents and the process have been optimized iteratively. Basically, improvements of membranes have been performed to increase the functionality and the water permeability through support layer. The systems used for the demonstrations are 1. CNC BE cartridges (4 units); Type of water: Leather Industry Waste Water.; Contaminant removal: Dyes.2. CNF TEMPO cartridges (10 units); Type of water: Drinking Water.; Contaminant removal: Hardness3. CNF CATIONIC cartridges (2 units); Type of water: Urban Waste Water; Contaminant removal: Nitrates.

The trials were positive for the removal of dyes and nitrates at the industrial sites and is used for the final demonstration.

Four CNC BE cartridges were tested, to remove dyes from waste water, in the Prototype First Generation placed in the Leather Industry (INCUSA), Valencia Spain. For Dyes removal, the Hybrid CNCBE/Sludge 124 gsm (Roll 4), worked well because it was able to reduce the turbidity 61,4 %. Moreover, this one combined with the ozone technology, reached 89,7 % of turbidity reduction. Two CNF CATIONIC cartridges were tested to remove nitrates from urban waste water in a phytoremediation plant located in Projar Group, Valencia, Spain. The test results showed that Sludge/cat CNF cartridge was able to reduce the nitrates concentration 82 % and was considered most successful. See Video https://www.youtube.com/watch?v=RNV0fccdMHs, uploaded in Nanoselect website.

Cost analysis Cost was calculated for the Nanoselect membrane processing at pilot scale and module processing and are given below. Table 3. Cost of Pilot scale processing of membranes

Membrane scale up: The production of current membranes on the market are depending on the scale-of-production but a general initial price target for the new membranes should be less than 15 €/m2. The membrane production costs can be separated in two main cost factors:• Investment into a new pilot production line• Material and operating cost Based on the above, it reasonable to assume that the cost of the new membrane will be in-line with current membranes and thus competitive from a cost point of view. The investment for a pilot production machine should be justifiable based on the market potential give.

Module scale up: The modules proposed in the Nanoselect project are from production point of view minor modifications of the current commercial spiral wound modules. Hence, the production can be achieved with current production equipment and thus the cost structure is similar to current spiral wound modules on the market. Moreover, the Nanoselect membranes have been manufactured with the standard size cartridge, which makes it easier to introduce the product in the market: No extra cost and no additional/special requirements are needed for the installation of this type of cartridges.

Nanoselect technology use for water purificationNanoselect membranes and modules once scaled up is expected to be competent in the market, for suspended solids (compared to PP filters) for dyes ( compared to PP filers +activated carbon) and for nitrates ( compared top filters + resins). See table below.

Table 5. The comparison of Nanoselect modules with current market solutions

Market analysis The market analysis of nanocellulose was conducted by LTU and Processum. The world nanocellulose production capacity is anticipated to reach 800 tons by the year 2017. The processing of CNF and CNC from industrial side streams scale up in Nanoselect have great potential for commercilaization due to its cost effectiveness compared to other commercial grades available today. Market analysis was done for Nanoselect membranes and modules (Alfalaval) and for water related services based on Nanoselect technology (Alfalaval)The focus of the Nanoselect project is in line with current and future market needs by developing no-/low-fouling membranes based on sustainable membrane materials. The importance of the Nanoselect project is also underlined by key objective of the market drivers of the global membrane market. Thus, the Nanoselect project is supporting the key objectives of the market by focusing on membranes and modules for water as well as food/pharmaceutical application. Hence, the membrane market covered by the Nanoselect project accounts for approx. 1/3 of the total membrane market worth 8-10 billion Euros, which will still experience average annual growth rates of 8 % per years for the coming years. The key future applications are:• Pre-treatment of in-take water before reverse osmosis• Post-treatment of process water before discharge, e.g. removal of metals• High fouling application in the food and pharmaceutical industry, e.g. protein fouling. Considering that the main challenges of the market – fouling and sustainability – are covered by this project, the potential outcome of the project can have a significant impact on the market. Furthermore, the development of improved membrane modules is closely linked to current market modules, which will ease the market introduction and allows these modules to enter the important module replacement market. Hence, both membranes and modules developed in the project have the potential to cover a significant proportion of the current membrane and module market.

The market for the modules once scale up is remarkably high , especially for nitrates. The estimated market for Nanoselect CNF Cationic modules in Spain to remove the solids and the nitrates is 24.703.200 €./per day and the profit would be 4.940.640 ( about 20 % of the sales). The estimated market in Spain for Nanoselect CNCBE modules is 8.212.500 €/per year and the profit expected is 1.642.500 €/per year Nanoselect membranes and modules once scaled up will be competent in the market, for suspended solids (compared to PP filters) for dyes (compared to activated carbon) and for nitrates (compared to resins) . The market for the modules in water purification sector is remarkably high , especially for nitrates. The use of Nanoselect nitrate filters can be considered as highly successful as they have an added advantage of disposal as fertilizer. The product can be sold at a good profit and scaling up the process will lead to reliable margin and return of investment. The estimated market for Nanoselect CNF Cationic modules in Spain to remove the solids and the nitrates is 24.703.200 €./per day and the profit would be 4.940.640 ( about 20 % of the sales). Easy introduction of Nanoselect modules in the market is envisioned as these modules have been manufactured to fit the standard size cartridge. No extra cost is required to place the membrane inside the standard vessels and no additional/special requirements are needed for their installation which can make the market entry easier

ConclusionNanoSelect project successfully designed, develop and optimized novel bio-based nanostructured polymer based membranes/adsorbents/filters for removal of ocontaminants as metalions, dyes and nitrates form water, taking advantage of functionalities on like nanocellulose, nanochitin and combinations thereof.

Membrane assemblies and modules based on selected modified and unmodified nanocellulose were validated for removal of water contaminants as well as recovery of metal ions and reuse of membrane modules. The demonstration of the modules and prototypes from Nanoselect was successful at the industrial sites and effectively reduced nitrates, dyes and suspended solids. Nanocellulose based membranes were found to be inherently antifouling due to its hydrophilic nature and can be used as antifouling membranes without additional surface functionalization. Acid wash can be used for recovery of metal ions and the reuse of membranes after metal adsorption. Moreover, incineration can be carried out to recover to 100% of the adsorbed heavy metals, at the end-of-life. . Nitrates on the other hand after adsorption can be effectively received as fertilizer via composting.

Cost analysis showed that the use of Nanoselect nitrate filters have an added advantage over commercial membranes of due to adsorption efficiency as well as disposal potential as fertiliser. It was also clear that the membranes and modules from Nanoselect project once scaled up will lead to reliable margin and return of investment. The technology transfer to industries can be done effectively as the Nanoselect module design with a standard size which makes it easy to introduce and install these in the current market and existing installations.

NanoSelect project has resulted in new know-how on surface interaction of nanocellulose/nanochitin with different molecules, atoms and, ions, and is also expected to open up new applications and increased utilization of these bio based nanomaterials as functional materials, beyond water treatment application.

Potential Impact:The successful completion of the proposed project is expected to impact in the water treatment in developing, transitional countries as well as the industrialised countries.

Commercial Impact: Nanoenabled biobased membranes developed using NanoSelect technology will have pore sizes ranging from those in reverse osmosis to up to those in ultrafiltration. The aim is to have high flux which reduces pressure and thereby energy consumption while keeping the high selectivity efficiency due to surface adsorption. The market position of the new membranes from NanoSelect will be in the range of nanofiltration membranes and reverse osmosis membranes and is expected to have pressure requirements as low as that of ultarfiltration membranes. This new technology is therefore expected to have impact the market share of reverse osmosis (RO), nanofiltration (NF) and ultrafiltration membranes (UF). Alfalaval , the membrane producer partnering in Nanoselect has high interest in the developed technology and is expected to provide them a competitive edge in biobased membrane market .The focus of the Nanoselect project is in line with current and future market needs by developing no-/low-fouling membranes based on sustainable membrane materials. The importance of the Nanoselect project is also underlined by key objective of the market drivers of the global membrane market. Thus, the Nanoselect project is supporting the key objectives of the market by focusing on membranes and modules for water as well as food/pharmaceutical application. Hence, the membrane market covered by the Nanoselect project accounts for approx. 1/3 of the total membrane market worth 8-10 billion Euros, which will still experience average annual growth rates of 8 % per years for the coming years. The key future applications are:• Pre-treatment of in-take water before reverse osmosis• Post-treatment of process water before discharge, e.g. removal of metals• High fouling application in the food and pharmaceutical industry, e.g. protein fouling. Considering that the main challenges of the market – fouling and sustainability – are covered by this project, the potential outcome of the project can have a significant impact on the market. Furthermore, the development of improved membrane modules is closely linked to current market modules, which will ease the market introduction and allows these modules to enter the important module replacement market. Hence, both membranes and modules developed in the project have the potential to cover a significant proportion of the current membrane and module market

Recovery of heavy metals, high efficiency decentralised water cleaning, high adsorption rates, high adsorption selectivity, reusable antifouling or low fouling surfaces and compost-ability at the end-of-life are some of the additional attributes of the membranes/filters and adsorbents developed in this project. The market for the modules in water purification sector is remarkably high, especially for nitrates. The use of Nanoselect nitrate filters can be considered as highly successful as they have an added advantage of disposal as fertilizer. The product can be sold at a good profit and scaling up the process will lead to reliable margin and return of investment. The estimated market for Nanoselect CNF Cationic modules in Spain to remove the solids and the nitrates is 24.703.200 €./per day and the profit would be 4.940.640 ( about 20 % of the sales). The most promising membranes for capture of metal ions, nitrates and dyes are made into spiral wound modules or cartridge modules with surface flow mode or crossflow mode. The new nanoenhanced membranes and modules developed in NanoSelect is being first tested on site by Acondaqua, which gives this SME a commercial and knowledge-based edge in the novel water cleaning technology based on biobased nanoparticles. The SME will aim industrial water as well as domestic water quality improvement/reuse that can significantly increase their client base and their turnover.

Nanocellulose and nanochitin from the residues of forest industries and aqua culture as the raw material for membrane/filter application will lead to value-add for these natural resources and will have positive impact on the economy of these industry sectors. The introduction of new processes to utilize residues and side-streams from forest-based industries (cellulose production ad bioethanol production) will open up new markets and value-add to forest resources. This is expected to lead to a new value-add to forest based industries like for eg. pulp and paper mills, cellulose producers and bioethanol industries. The market analysis of nanocellulose was conducted by LTU and Processum. The world nanocellulose production capacity is anticipated to reach 800 tons by the year 2017. The processing of CNF and CNC from industrial side streams scale up in Nanoselect have great potential for commercilaization due to its cost effectiveness compared to other commercial grades available today.

Socio-Economic ImpactThe current project addresses the removal of one or more of water pollutants and will have long-term impact on human health and quality of life. This project works towards this objective and leads to new products based on green-nanotechnology in the form of nanomembranes/filters/adsorbents for water purification which is expected to be more efficient, cost effective, sustainable, low fouling and biodegradable than the currently available products. Globally, these products will provide environmental friendly and cheap solution for water recycling and removal/ recovery of heavy metal ions, fertilizers, drugs and pesticides from industrial effluents. The improvement envisoned in the quality of surface and ground water, initially at Europe and then on a global level, will have far reaching impact on environment. The projects vision is a sustainable use of water, which is an invaluable natural resource.

The Project positively impacts environmental aspects at several fronts, starting from raw materials used, processes used, products developed and targeted applications that promote a cleaner environment by developing high efficiency products for water purification. Water cleaning solutions developed in the project will help companies, regions, and cities to meet water efficiency standards in urban, agricultural and industrial areas (INSPIRE Directive). The project addresses directly or indirectly the water policy of the European Union, which is primarily codified in three directives at different levels: - The Urban Waste Water Treatment Directive (91/271/EEC) of 21 May 1991 concerning discharges of municipal and some industrial waste waters;- The Drinking Water Directive (98/83/EC) of 3 November 1998 concerning potable water quality;- Water Framework Directive (2000/60/EC) of 23 October 2000 concerning water resources management.

Social ImpactsThe following social impacts are expected: projects vision is a sustainable use of water, which is an invaluable natural resource• water resource management and the environmental protection aspects of process industries, ,Government/Public sector as well as agricutural sectors with in Europe. • The recycling of chemicals and recovery of heavy metal ions also will positively impact the environment • Green and environmental friendly membranes and porous filter produced from renewable resources and (modified) nanocellulose from industrial and/or agricultural waste streams contributes to environmentally benign products and services.• The process of isolation of nanomaterial involves forestry industry residues, which further promotes ‘green nanotechnology’ and sustainable use of natural resources and contributes to emerging environmental standards with in Europe.The following technologies are tested successfully in industries and have a direct impact on the water quality in the process, effluents and the nearby waterbodies.

• Dyes removal: Nanoselect anionic membranes and modules worked well for removal of dyes from tannery and also because it was able to reduce the turbidity by 61,4 %. Moreover, this one combined with the ozone technology, reached 89,7 % of turbidity reduction. • Nitrate removal: CNF CATIONIC modules were tested and the test results showed that the roducts was able to reduce the nitrates concentration 82 % and was considered most successful.

Nanoselect membranes and modules once scaled up is expected to be competent in the market, for suspended solids (compared to PP filters) for dyes (compared to PP filers +activated carbon) and for nitrates (compared top filters + resins). Easy introduction of Nanoselect modules in the market is envisioned as these modules have been manufactured to it the standard size cartridge. No extra cost is required to place the membrane inside the standard vessels and no additional/special requirements are needed for their installation, which can make the market entry easier. It is possible to produce Nanoselect membrane and customise the functionality for targeted contaminants by changing the type of the nanocellulose material. The membrane and module processing once scaled up can be effectively adopted by industries with dyes, nitrates, metal ions and suspended solids contamination. The recycling of chemicals and recovery of heavy metal ions also will positively impact the environment. NanoSelect aims to provide a cheaper and safer route for water management and enable the efficient utilization of surface water and ground water near the agricultural lands, mines and different chemical based industries.

A collaboration between paper making industry and membrane industry can be recommended as a successful route for the optimization of the membrane and module processing and a fast market entry which will create job opportunities in these sectors and well as water treatment service market. Technology transfer to industries can be done effectively due to the Nanoselect module design developed with a standard size so that it is easy to introduce and install it in the current market and existing installations.

Scientific impact: Nanoselect project has a pioneering role in the commercial utilisation of bio based nano crystals and nano fibres as functional membranes for cleaning water .The use of adsorption as the key mechanism of water purificationand the process scale up of biobased nanoparticles, membranes and filters with controlled functionality and homogeneity developed based on multidisciplinary research and development will lead to new high technology products based on green nanotechnology .The IP generated from the project will be used as background knowledge for other national and EU projects by all partners to secure more research funding. See the details of the peer-reviweed jounal publications, conference contribution, disserations etc from the project which enabled disseminating the know-how developed in the project to the scientific community, industries and other stake holders and the general public.

An important outcome of this project has been the training of researchers and Ph.Ds. in the cutting edge of green technology. This will give rise to a new generation of scientists for the world endowed with the potential to develop green materials for the future. Further more, the know-how developed in BioPure will open up new applications and increase utilization of this bio based nanomaterial’s as functional materials, and extend their usage beyond water treatment applications (e.g., purification of gaseous mixtures, cleaning of exhaust fumes from automobiles or factories, separation of proteins, drugs, DNA etc.)

DisseminationDissemination and exploitation activities was carried out in an organized manner in order to not infringe any potential knowledge protection. Nnaoselect website, press releases, demonstrations , conferences, workshops seminars, peer-reviewed journal articles, popular science articles, PhD/ master theses, LinkedIin and Facebook profiles etc. were used as dissemination tools for effective outreach. Active involvement in European networks as nano4 water also supported the dissemination activity.

Dissemination plan was drafted and reported in M25 and up dated in M36 and M48.

- DISSERTATIONS• Liu, P. May 2014 Luleå University of Technology: Nanopolysaccharides for adsorption of heavy metal ions from water . d96f82e6-a2fb-47ce-8d06-f28702d2589f.html • • Karim Z., November 2014, Luleå University of Technology: Processing and characterization of membranes based on cellulose nanocrystals for water purification: Nanocellulose as functional entity, 5897fdde-5366-4214-9832-e7062799c27e.html

• Nano4 water activities• Participation in 2nd, 3rd and 5th Nano4water workshops• The 4th Dissemenation workshop for Nano4water was hosted by NanoSelect, in Stockholm during April 23-24, 2014• Nanoselect website Nanoselect website was established during M4 and the website is updated regularly. Nanoselect website acts as a venue for publishing the activities and achievements of the project. The website will be maintained for 2 years after the closing of the project (www.nanoselect.eu)• Nanoselect facebook page Nanoselect face book page was established in 2013 and will be used to share information that can be public. https://www.facebook.com/Nanoselect-440025132780007/

- Exploitation:

The details of the exploitable results are available under Plan for Using and Disseminating of Foreground document (PUDF) and the final updated version is available in M48.

These results are reviewed during the project course and at the project end to finalise the exploitation strategies

Expliotable result 1.

Biobased nanoparticles from industrial residues for water cleaning by selective adsorption- Estimated time to market ; 2-3 years- Chemistry used not protectable- Ready for pilot scale processing( predominantly following well-known and published strategies for cellulose and chitin nanofibers and nanocrystalsas acid hydrolysis, steam explosion, delignifcation, mechanical processing, chemical processing)- Actions needed to facilitate market entry:- Process optimization and demonstration in pilot scale- Up-scaling to a competent price - Market pull missing ( Economic production compared to benchmark materials has to be shown).

Expliotable result 2. Modified bio-based nanoparticles by chemical or enzymatic methods for removal of contaminants (heavy metal ions, dyes) from water by selective adsorption

- Estimated time to market 3 to 5 years)- Chemistry used not protectable- Implementaion of functionalisation in industry scale is feasible – predominantly following well-known modification strategies (Chemical and enzymatic TEMPO-oxidation, esterification with anhydrates, phosphorylation)- Actions needed to facilitate market entry:- Up-scalability to a reasonable price – market pull missing – economic production compared to benchmark materials has to be shown- Green aspect of the production of modified nanofibers to be compared and benchmarked- Efficiency for specific contaminant removal to be compared and benchmarked- Recyclability of modified fibers and recovery of contaminants to be demonstrated- Demonstration in real life application

- Expliotable result 3. Biobased membranes and porous filter media for water purification

- Estimated time to market : 3 to 5 years- Technology is not protectable, But the exact formulation and process methodology can be protected One patent is in discussion and agreement to be executed on ownership to clearly define the IP right One patent is filed by LTU on layered membranes for removal of metal ions - Hybrid/layered nanopapers can be produced in large scale with commercial papermaking machine.- Membranes with different configurations are easy to produce via simple filtration technique.; They are easy to handle and can be produced with different functional nanocelluloses (CNCBE, Cationic CNF, TEMPO etc.).- Actions needed to facilitate market entry:- Up-scalability to a reasonable price to be demonstarted- Membrane homogeneity to be optimized via scale up- Green aspect of the production of modified membranes to be compared and benchmarked

In addition to commercial exploitation, the IP generated from the project will be used as background for other national and EU projects by all partners. See the details of the proposals where Nanoselect foreground is used . About 6 proposals were are submitted by partners in national and H2020 projects, where Nanoselect results are used as background. A pilot scale project under H2020 to make the membranes and modules ready for market is under discussion.